CH524585A - 19-alkyl steroids - Google Patents
19-alkyl steroidsInfo
- Publication number
- CH524585A CH524585A CH1782570A CH1782570A CH524585A CH 524585 A CH524585 A CH 524585A CH 1782570 A CH1782570 A CH 1782570A CH 1782570 A CH1782570 A CH 1782570A CH 524585 A CH524585 A CH 524585A
- Authority
- CH
- Switzerland
- Prior art keywords
- alkyl
- delta4
- steroids
- acyloxy
- formula
- Prior art date
Links
- 125000000304 alkynyl group Chemical group 0.000 claims abstract 2
- 150000003431 steroids Chemical class 0.000 claims description 8
- 125000004423 acyloxy group Chemical group 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- RJKFOVLPORLFTN-LEKSSAKUSA-N Progesterone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](C(=O)C)[C@@]1(C)CC2 RJKFOVLPORLFTN-LEKSSAKUSA-N 0.000 abstract description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 230000035558 fertility Effects 0.000 abstract description 2
- 229960003387 progesterone Drugs 0.000 abstract description 2
- 239000000186 progesterone Substances 0.000 abstract description 2
- 101100241859 Mus musculus Oacyl gene Proteins 0.000 abstract 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 abstract 1
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- -1 methoxy, ethoxy Chemical group 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000000825 pharmaceutical preparation Substances 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 102000006771 Gonadotropins Human genes 0.000 description 1
- 108010086677 Gonadotropins Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000002622 gonadotropin Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 238000007911 parenteral administration Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J1/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, not substituted in position 17 beta by a carbon atom, e.g. estrane, androstane
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J75/00—Processes for the preparation of steroids in general
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Steroid Compounds (AREA)
Abstract
19-Alkyl steroids of general formula (I) where R' = H or C1-6-alkyl; R" = HO, AcylO or C1-6-alkoxy; R3 = H, C1-6-alkyl or R4 which = C2-6-alkenyl or alkynyl. R(when R' = alkyl and R3 = H or 1-6 C alkyl) = 3-keto-DELTA4,6 or -DELTA1,4,6; 3-acyloxy-DELTA3,5 or -DELTA2,4,6; 3-alkoxy-DELTA3,5 or -DELTA3,5,7; 3-OH (or OAlk or OAcyl)-DELTA4 or -DELTA4,6; And, when R' = H and R3 = R4, R = 3-keto-DELTA4 or -DELTA1,4; Preferred are R3 = R4; R = 3-OH(or Oalk or OAcyl)-DELTA4 or -DELTA4,6. Hormonally active compds. They affect the body gonadotrophin and hinder the action of progesterone. Used for fertility control.
Description
Verfahren zur Herstellung von 19-Alkylsteroiden Die Erfindung betrifft ein Verfahren zur Herstellung von 19-Alkylsteroiden der Formel
EMI1.1
oder von zl -Derivaten von Steroiden der Formel Ia bzw. vor d 6-Derivaten von Steroiden der Formel Ib, in welchen For meln R Hydroxy oder Acyloxy, R1 Wasserstoff oder C16- Alkyl, R2 Hydroxy, Acyloxy oder Cl¯d-Alkoxy und R3 Wasserstoff, C,,-Alkyl, C2-Alkenyl oder C2¯6-Alkinyl bedeuten, wobei jedoch mindestens in einer der Stellungen 3 und 17 eine Acyloxygruppe anwesend ist.
Eine bevorzugte Gruppe von erfindungsgemäss erhältlichen Verbindungen weisen in der 17a-Stellung einen Alkenyl- oder Alkinylrest auf.
Das erfindungsgemässe Verfahren ist dadurch gekennzeichnet, dass man ein Steroid der Formel Ia bzw. Ib, worin jedoch mindestens in einer der Stellungen 3 und 17 eine Hydroxygruppe anwesend ist, oder ein zl l-Derivat eines Steroids der Formel Ia bzw. ein d 6-Derivat eines Steroids der Formel Ib acyliert.
Die vorstehend verwendeten Bezeichnungen C1-6-A1- kyl, C2-Alkenyl und C,,-Alkinyl beziehen sich auf solche Kohlenwasserstoffreste, die 14 bzw. 26 C-Atome enthalten und die geradkettig oder verzweigt sein können. Beispiele für C1¯6-Alkyl sind Methyl, Äthyl, Propyl, Isopropyl, Butyl, Isobutyl, tert.-Butyl, Pentyl und Hexyl. Beispiele für C26-Alkenyl sind Vinyl, Allyl und Methallyl. Beispiele für Gi6-Alkinylreste sind Äthinyl, Propinyl und Propargyl.
Eine durch das Symbol R2 dargestellte Acyloxygruppe sowie eine 3-Acyloxygruppe enthalten vorzugsweise den Rest einer gesättigten oder ungesättigten, aliphatischen oder aromatischen Carbonsäure mit 1-10 Kohlenstoffatomen. Bei spiele solcher Säuren sind Essigsäure, Propionsäure, Capron säure, Pivalinsäure, Buttersäure, Isobuttersäure und Benzoe säure. Beispiele für eine C,,-Alkoxygruppe sind Methoxy, Äthoxy und tert.-Butoxy.
Die erfindungsgemässe Acylierung einer 3- oder 17-Hydroxygruppe eines der genannten 19-Alkylsteroide kann in an sich bekannter Weise, zum Beispiel mittels eines reaktionsfähigen Acylderivats, wie eines Acylanhydrids oder -halogenids, in Gegenwart einer Base, wie Pyridin, erfolgen.
Die Verfahrensprodukte sind hormonal wirksam. Sie beeinflussen den Gonadotropin-Haushalt des Körpers und hemmen die Wirkung von Progesteron. Sie können als Mittel zur Fertilitätskontrolle Verwendung finden, z.B. in Form pharmazeutischer Präparate, (Dosiseinheit 50 ,ug-10 mg) welche sie in Mischung mit einem für die enterale oder parenterale Applikation geeigneten pharmazeutischen, organischen oder anorganischen inerten Trägermaterial enthalten. Die pharmazeutischen Präparate können in fester Form oder in flüssiger Form vorliegen. Gegebenenfalls enthalten sie Hilfsstoffe, wie Konservierungs-, Stabilisierungs-, Netz- oder Emulgiermittel, Salze zur Veränderung des osmotischen Druckes oder Puffers. Sie können auch noch andere therapeutisch wertvolle Stoffe enthalten.
Beispiel 1
1 g 17a-Äthinyl-17ss-hydroxy-19-methyl-androsta-1,4,6- trien-3-on werden in einem Gemisch von 10 ml Acetanhydrid und 10 ml Pyridin gelöst und über Nacht bei 100" gehalten.
Man dampft die Lösung im Vakuum ein und reinigt den Rückstand durch Filtration an Aluminiumoxid II. Das Eluat wird eingedampft und aus Aceton/Hexan umkristallisiert, wobei man 1 g 17ss-Acetoxy-17a-äthinyl-19-methyl-androsta-1,4,6-trien-3-on erhält. Schmelzpunkt 271-72 (aus Aceton/Hexan) UV: 8246 = 16000; [a]589=36 (c = 0,1 in Dioxan).
Beispiel 2
130 mg 3ss,17ss-Dihydroxy-19-äthyl-17α-äthinyl-androst- 4-en werden in 2 ml Acetanhydrid und 2 ml Pyridin gelöst und während 4 Stunden bei Zimmertemperatur stehengelassen. Das Gemisch wird mit Benzol mehrmals im Vakuum abgedampft und der Rückstand über Aluminiumoxid filtriert. Nach Chromatographie des erhaltenen Rohproduktes an 20 g Silicagel mit Hexan/Aceton 9:1 erhält man 80 mg 3ss-Acetoxy- 19-äthyl-17a-äthinyl- 17ss-hydroxy-androst-4-en in Form eines farblosen Schaumes. [a]589 =-76 (c= 0,1 in Dioxan) .
Process for preparing 19-alkyl steroids The invention relates to a process for preparing 19-alkyl steroids of the formula
EMI1.1
or of zl derivatives of steroids of the formula Ia or before d 6 derivatives of steroids of the formula Ib, in which formulas R hydroxy or acyloxy, R1 hydrogen or C16 alkyl, R2 hydroxy, acyloxy or Cl¯d alkoxy and R3 denotes hydrogen, C1-alkyl, C2-alkenyl or C2¯6-alkynyl, but an acyloxy group is present in at least one of positions 3 and 17.
A preferred group of compounds obtainable according to the invention have an alkenyl or alkynyl radical in the 17a position.
The process according to the invention is characterized in that a steroid of the formula Ia or Ib, in which, however, a hydroxyl group is present in at least one of the positions 3 and 17, or a zl l derivative of a steroid of the formula Ia or ad Acylated derivative of a steroid of the formula Ib.
The terms C1-6-alkyl, C2-alkenyl and C1- alkynyl used above refer to those hydrocarbon radicals which contain 14 or 26 carbon atoms and which can be straight-chain or branched. Examples of C1¯6-alkyl are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl and hexyl. Examples of C26 alkenyl are vinyl, allyl and methallyl. Examples of Gi6-alkynyl radicals are ethynyl, propynyl and propargyl.
An acyloxy group represented by the symbol R2 and a 3-acyloxy group preferably contain the remainder of a saturated or unsaturated, aliphatic or aromatic carboxylic acid having 1-10 carbon atoms. In games of such acids are acetic acid, propionic acid, caproic acid, pivalic acid, butyric acid, isobutyric acid and benzoic acid. Examples of a C1-alkoxy group are methoxy, ethoxy and tert-butoxy.
The acylation according to the invention of a 3- or 17-hydroxy group of one of the 19-alkyl steroids mentioned can be carried out in a manner known per se, for example by means of a reactive acyl derivative such as an acyl anhydride or halide, in the presence of a base such as pyridine.
The process products are hormonally effective. They influence the body's gonadotropin balance and inhibit the effects of progesterone. They can be used as a means of fertility control, e.g. in the form of pharmaceutical preparations (dose unit 50, μg-10 mg) which they contain in a mixture with a pharmaceutical, organic or inorganic inert carrier material suitable for enteral or parenteral administration. The pharmaceutical preparations can be in solid form or in liquid form. They may contain auxiliaries, such as preservatives, stabilizers, wetting agents or emulsifiers, salts for changing the osmotic pressure or buffers. They can also contain other therapeutically valuable substances.
example 1
1 g of 17a-ethynyl-17ss-hydroxy-19-methyl-androsta-1,4,6-trien-3-one are dissolved in a mixture of 10 ml of acetic anhydride and 10 ml of pyridine and kept at 100 "overnight.
The solution is evaporated in vacuo and the residue is purified by filtration on aluminum oxide II. The eluate is evaporated and recrystallized from acetone / hexane, 1 g of 17ss-acetoxy-17a-ethinyl-19-methyl-androsta-1,4, 6-trien-3-one receives. Melting point 271-72 (from acetone / hexane) UV: 8246 = 16,000; [a] 589 = 36 (c = 0.1 in dioxane).
Example 2
130 mg of 3ss, 17ss-dihydroxy-19-ethyl-17α-ethinyl-androst-4-en are dissolved in 2 ml of acetic anhydride and 2 ml of pyridine and left to stand for 4 hours at room temperature. The mixture is evaporated several times in vacuo with benzene and the residue is filtered through aluminum oxide. After chromatography of the crude product obtained on 20 g of silica gel with hexane / acetone 9: 1, 80 mg of 3ss-acetoxy-19-ethyl-17a-ethinyl-17ss-hydroxy-androst-4-ene are obtained in the form of a colorless foam. [a] 589 = -76 (c = 0.1 in dioxane).
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1782570A CH524585A (en) | 1968-05-15 | 1969-04-25 | 19-alkyl steroids |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH720068A CH502327A (en) | 1968-05-15 | 1968-05-15 | Process for the preparation of 19-alkyl steroids |
| CH1782570A CH524585A (en) | 1968-05-15 | 1969-04-25 | 19-alkyl steroids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH524585A true CH524585A (en) | 1972-06-30 |
Family
ID=4321433
Family Applications (5)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1782270A CH507926A (en) | 1968-05-15 | 1968-05-15 | 19-alkyl steroids |
| CH720068A CH502327A (en) | 1968-05-15 | 1968-05-15 | Process for the preparation of 19-alkyl steroids |
| CH1782470A CH507923A (en) | 1968-05-15 | 1969-04-25 | 19-alkyl steroids |
| CH1782570A CH524585A (en) | 1968-05-15 | 1969-04-25 | 19-alkyl steroids |
| CH1782370A CH507925A (en) | 1968-05-15 | 1969-04-25 | 19-alkyl steroids |
Family Applications Before (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1782270A CH507926A (en) | 1968-05-15 | 1968-05-15 | 19-alkyl steroids |
| CH720068A CH502327A (en) | 1968-05-15 | 1968-05-15 | Process for the preparation of 19-alkyl steroids |
| CH1782470A CH507923A (en) | 1968-05-15 | 1969-04-25 | 19-alkyl steroids |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1782370A CH507925A (en) | 1968-05-15 | 1969-04-25 | 19-alkyl steroids |
Country Status (9)
| Country | Link |
|---|---|
| AT (1) | AT290027B (en) |
| BE (1) | BE733017A (en) |
| CH (5) | CH507926A (en) |
| DE (1) | DE1924785A1 (en) |
| ES (1) | ES367281A1 (en) |
| FR (1) | FR2008589A1 (en) |
| GB (1) | GB1269234A (en) |
| IL (1) | IL32151A0 (en) |
| NL (1) | NL6907136A (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE632012A (en) * |
-
1968
- 1968-05-15 CH CH1782270A patent/CH507926A/en not_active IP Right Cessation
- 1968-05-15 CH CH720068A patent/CH502327A/en not_active IP Right Cessation
-
1969
- 1969-04-25 CH CH1782470A patent/CH507923A/en not_active IP Right Cessation
- 1969-04-25 CH CH1782570A patent/CH524585A/en not_active IP Right Cessation
- 1969-04-25 CH CH1782370A patent/CH507925A/en not_active IP Right Cessation
- 1969-05-04 IL IL32151A patent/IL32151A0/en unknown
- 1969-05-09 NL NL6907136A patent/NL6907136A/xx unknown
- 1969-05-13 GB GB24320/69A patent/GB1269234A/en not_active Expired
- 1969-05-14 AT AT460669A patent/AT290027B/en not_active IP Right Cessation
- 1969-05-14 BE BE733017D patent/BE733017A/xx unknown
- 1969-05-14 FR FR6915700A patent/FR2008589A1/fr not_active Withdrawn
- 1969-05-14 ES ES367281A patent/ES367281A1/en not_active Expired
- 1969-05-14 DE DE19691924785 patent/DE1924785A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CH507925A (en) | 1971-05-31 |
| ES367281A1 (en) | 1973-03-16 |
| AT290027B (en) | 1971-05-10 |
| IL32151A0 (en) | 1969-07-30 |
| BE733017A (en) | 1969-11-14 |
| CH502327A (en) | 1971-01-31 |
| FR2008589A1 (en) | 1970-01-23 |
| GB1269234A (en) | 1972-04-06 |
| DE1924785A1 (en) | 1969-11-20 |
| CH507923A (en) | 1971-05-31 |
| CH507926A (en) | 1971-05-31 |
| NL6907136A (en) | 1969-11-18 |
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